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WO2024035663A2 - Dioxyde de titane dans les batteries plomb-acide à cycle profond inondées - Google Patents

Dioxyde de titane dans les batteries plomb-acide à cycle profond inondées Download PDF

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Publication number
WO2024035663A2
WO2024035663A2 PCT/US2023/029677 US2023029677W WO2024035663A2 WO 2024035663 A2 WO2024035663 A2 WO 2024035663A2 US 2023029677 W US2023029677 W US 2023029677W WO 2024035663 A2 WO2024035663 A2 WO 2024035663A2
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WIPO (PCT)
Prior art keywords
positive
lead
tich
paste
rutile
Prior art date
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Ceased
Application number
PCT/US2023/029677
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English (en)
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WO2024035663A3 (fr
Inventor
Shawn PENG
Michael VERDE
Jesus Perez
Phil SHOLTES
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Trojan Battery Co LLC
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Trojan Battery Co LLC
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Filing date
Publication date
Application filed by Trojan Battery Co LLC filed Critical Trojan Battery Co LLC
Priority to EP23853262.6A priority Critical patent/EP4569555A2/fr
Publication of WO2024035663A2 publication Critical patent/WO2024035663A2/fr
Publication of WO2024035663A3 publication Critical patent/WO2024035663A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators

Definitions

  • the present invention relates to enhancing the service life of flooded deep cycle lead-acid batteries. More specifically, this present invention relates to the use of titanium dioxide (TiOz) in flooded deep cycle lead-acid batteries.
  • a lead-acid battery is a type of rechargeable battery that includes positive and negative electrodes and an electrolyte.
  • Typical electrodes in a lead-acid battery include an active material paste that is often mounted onto a grid plate.
  • the electrodes also include a separator between them.
  • the grid plates are primarily made of lead but often are combined with antimony, calcium, or tin to form alloys with improved mechanical characteristics. In deep discharge batteries, antimony is generally preferred to form the alloy with lead.
  • the active material pastes typically include lead oxide.
  • the electrolyte usually includes an aqueous acid solution, most often sulfuric acid (H2SO4).
  • a charge is applied, which converts the lead (Pb), lead oxide (PbO), tri-basic lead sulfate (3PbO.PbSO4.H2O) or tetrabasic lead sulfate (4PbO.PbSO4) of the positive side to lead dioxide (PbO2) and the lead (Pb), lead oxide (PbO) and tri-basic lead sulfate (3PbO.PbSO4.H2O) of the negative side to lead.
  • the chemical energy is stored in the lead on the negative electrode and the lead dioxide on the positive electrode, along with the aqueous sulfuric acid. Following formation, a lead-acid battery can be repeatedly discharged and charged.
  • Deep cycle lead-acid batteries differ from lead-acid starter (or high-current) batteries because of their ability to discharge most of their capacity (i.e., have a deep discharge) before needing to be recharged. Deep cycle batteries include thicker electrodes that deliver less peak current than starter batteries but can withstand frequent discharging and are therefore less susceptible to degradation.
  • Flooded lead-acid batteries are a type of deep cycle lead-acid battery that are also called vented lead-acid batteries or wet cell batteries. Flooded lead-acid batteries have thick, lead-based electrodes that are submerged in an excess of acid electrolyte. This type of battery requires certain maintenance. Some charging conditions may generate hydrogen and oxygen gas, along with the consumption of water in the electrolyte. Therefore, flooded lead-acid batteries need to be vented and have water occasionally added to them. This process may affect the specific gravity of the electrolyte, which must be periodically measured using a hydrometer, and undergo equalization to maintain desired values.
  • VRLA Valve Regulated Lead Acid
  • AGM Absorbent Glass Mat
  • gel type batteries do not require such maintenance, but are generally more expensive than flooded lead-acid batteries and require special chargers.
  • Active material shedding occurs when the bond between the active material and the plate grid weakens, causing a small portion of the active material to fall to the bottom of the battery, thus reducing its overall capacity.
  • the accumulation of active material at the base of a battery will eventually lead to battery failure, either due to the complete shedding of the active material or through the accumulation of the active material at the bottom of the casing, which may bridge to and short with the opposing charged plates within the battery.
  • Battery mossing occurs when active material builds up on the edges or at the bottom of the electrodes. Mossing occurs at a slow rate but in time may cause a short circuit between the electrodes. Mossing is worsened from overcharging, rough handling, or due to normal motion and vibration when installed in mobile equipment. If a battery is shorted, the battery will be discharged very quickly and will heat up due to the high current flow.
  • the present invention overcomes lead-acid battery performance and degradation issues by adding rutile titanium dioxide (TiCh) to positive paste, which enhances the positive active material (PAM) life during the cycling of flooded lead-acid batteries that use lead antimony alloy grids.
  • TiCh rutile titanium dioxide
  • the disclosed flooded deep cycle lead-acid battery includes at least one negative plate, at least one positive plate and an electrolyte.
  • the positive plate comprises a positive electrode grid made primarily of lead and a positive paste including a lead compound and TiCh additive.
  • the TiCb additive is rutile TiCh.
  • the rutile TiCh has a particle size less than 10pm.
  • the range of weight percent for the rutile TiCh is between 0.1% to 4% of oxide load.
  • the lead compound comprises lead oxide.
  • the positive electrode grid is made of a lead-antimony alloy.
  • the electrolyte includes sulfuric acid.
  • the positive paste comprises tribasic lead sulfate (3BS) while in other embodiments, the positive paste comprises tetrabasic lead sulfate (4BS). In other embodiments, the positive paste comprises both 3BS and 4BS.
  • the disclosed positive plate for a flooded deep cycle lead- acid battery comprises a positive electrode grid made primarily of lead and a positive paste comprising a lead compound and TiCh additive.
  • the disclosed process of manufacturing a positive active material paste for a flooded deep cycle lead-acid battery includes: directly adding TiO2 into a paste mixer with a lead compound to form a mix of positive additives; dry mixing the positive additives to form a dry mixture; adding water to the dry mixture; wet-mixing the water with the dry mixture to form a wet mixture; pasting and curing a positive electrode grid with the wet mixture.
  • the TiCh in the disclosed process is rutile TiCh.
  • the rutile TiCh has a particle size less than 10pm.
  • the range of weight percent for the rutile TiCh is between 0.1% to 4% of oxide load.
  • the lead compound in the disclosed process comprises lead oxide.
  • the positive electrode grid in the disclosed process is made of a lead-antimony alloy.
  • the positive paste in the disclosed process comprises 3BS, while in other embodiments the positive paste comprises 4BS. In other embodiments, the positive paste comprises both 3BS and 4BS.
  • Figure l is a schematic sectional view of a flooded deep cycle lead-acid battery according to one embodiment of the present invention.
  • Figure 2 compares the crystal structure of rutile TiO2 and P-PbO2.
  • Figure 3 is a chart comparing the characteristics of cured positive active material paste where TiCh has been added in accordance with some embodiments of the present invention to the characteristics of a cured control positive active material paste where no TiCh has been added.
  • Figure 4 is a graph comparing the specific discharge capacity of pasted working electrodes according to embodiments of the present invention to control electrodes in which no TiCh additives have been added to the positive active material pastes.
  • Figures 5-6 are graphs comparing the cycle life of flooded deep discharge lead- acid batteries according to embodiments of the present invention to control batteries in which no TiCh additives have been added to the positive active material pastes.
  • the disclosed invention delays the occurrence of positive active material shedding. Additionally, the disclosed invention significantly improves paste skeleton density and porosity, increases positive paste conductivity, and enhances the charging efficiency of the positive plate. Further, the disclosed invention lowers early battery life moss shorts.
  • FIG. 1 illustrates one embodiment of the disclosed invention.
  • Flooded deep cycle lead-acid battery 10 includes positive electrode grids 20 and negative electrode grids 30 and electrolyte solution 40. Separators 50 separate the positive electrode grids 20 and negative electrode grids 30 within battery case 55. Positive electrode grids 20 are each coated with positive active material paste 60 to form a positive plate 70. Negative electrode grids 30 are each coated with negative active material paste 80 to form a negative plate 90.
  • the positive electrode grids 20 are connected via a positive current collector 100 and the negative electrode grids 30 are connected via a negative current collector 110.
  • Positive and negative battery terminal posts 120, 130 extend from the battery to provide external electrical contact points for charging and discharging the battery.
  • the battery 10 includes a vent 140 to release excess gas that is produced during charge cycles. A vent cap 150 prevents the electrolyte solution from spilling out of the battery 10. It should be clear to one of ordinary skill in the art that the invention can be applied to both single and multiple cell batteries.
  • the electrolyte solution 40 includes an aqueous acid solution. Further, in some embodiments, the electrolyte solution 40 includes sulfuric acid (H2SO4).
  • Rutile TiCh is one form of TiCh. Rutile TiCh is more stable and has a higher absorption rate than other forms. As shown in Figure 2, rutile TiCb is tetragonal in structure and shares an identical space group to P-PbO2 positive active material.
  • the positive active material paste 60 includes lead oxide and rutile TiCh.
  • the rutile TiCh may have a particle size less than 10pm.
  • the range of weight percent for the rutile TiCh may be between 0.1% to 4% of oxide load.
  • battery 10 with an improved positive plate 70 containing rutile TiCh with a weight percent between 0.1% to 4% of oxide load maintains a higher state of charge (SoC) level and includes better charging acceptance than a control battery 10 lacking the rutile TiCh additive to the positive active material paste 60.
  • SoC state of charge
  • battery 10 with an improved positive plate 70 containing rutile TiCh with a weight percent between 0.1% to 4% of oxide load maintains a lower positive half-cell potential than a control battery 10 lacking the rutile TiCh additive to the positive active material paste 60, which avoids aggressive Ch gassing and positive grid corrosion.
  • the paste preparation process for positive plates 70 and negative plates 90 results in particles of definite shape and composition. These particles are spread on the electrode grids 20, 30, cured to interlock the particles into a porous mass, and converted electrochemically into active material to produce the electrode plates 70, 90 of the lead acid battery cell 10.
  • the plates 70, 90 then have an active surface, definite porosity, and a hard active mass and connection to the grid. The porosity of the active materials is determined by the size of the paste particles.
  • Paste mixing may consist of two stages: dry mixing and wet mixing.
  • the dry mixing mixes the dry lead oxide with positive paste additives or negative paste additives.
  • the lead oxide may be composed of PbO and Pb produced by a ball milling or Barton milling process.
  • the type and amount of additives depends on the specific formula used, which may differ between manufacture and application.
  • a defined volume of water is added into the mixer to start the wet mixing process.
  • a certain volume of sulfuric acid with a defined specific gravity, may be added into the mixer to continue mixing until the final paste-like material has been achieved with a targeted paste density, viscosity, or other required properties.
  • the amount of time spent on each step will be controlled, and peak temperature will be controlled as well.
  • the rutile TiCh may be added in the paste mixing process. Further, in some embodiments, the rutile TiCh may be added into a paste mixer with lead oxide before dry mixing as a positive additive. Water may then be added to the dry mixture and the mixture may be wet-mixed for a certain amount of time. After wet-mixing, acid is added and mixing continues.
  • the paste 60 may then be placed in a pasting machine, which will press the paste 60 into the electrode grid 20.
  • the paste 60 may be pressed into the empty space around the wires in the electrode grid 20.
  • the electrode grids 20 and 30 are primarily made of lead but are combined with antimony.
  • the electrode grid 20 is referred to as a plate 70.
  • Rollers may flatten the plate 70 surfaces.
  • the plate 70 may then be cured to form an uninterrupted, strong porous mass that is tightly bound to the grid 20.
  • small crystals in the paste may dissolve while big crystals may grow in size. Water between the particles may evaporate, resulting in tribasic lead sulfate (3BS) or tetrabasic lead sulfate (4BS) crystals and PbO particles interconnecting to form a strong skeleton.
  • 3BS tribasic lead sulfate
  • 4BS tetrabasic lead sulfate
  • the curing process may consist of two stages: the wet stage and the drying stage.
  • the curing chamber will maintain a certain temperature (in some embodiments 105-150° F with high relative humidity (in some embodiments over 90% and in some embodiments even higher than 95%).
  • the wet curing stage can last from a few hours to tens of hours, depending on the different manufacture processes.
  • the drying stage may be used to fully dry the paste 60 material on the plate 70. This stage may have very low relative humidity (RH) and last from around 10 hours to over 40 hours, depending on plate design and production process design.
  • RH relative humidity
  • control 3BS positive active material paste 60 with no TiCh additives has a skeleton density ranging from 7.694 to 7.738 g/cc
  • 3BS positive active material paste 60 with 1% TiCh additives has a skeleton density ranging from 8.046 to 8.096 g/cc.
  • control 4BS positive active material paste 60 with no TiCh additives has a skeleton density ranging from 7.606 to 7.648 g/cc
  • 4BS positive active material paste 60 with 1% TiCh additives has a skeleton density ranging from 8.013 to 8.032 g/cc.
  • TiCh additives can therefore increase the positive active material paste 60 skeleton density.
  • control 3BS positive active material paste 60 with no TiCh additives has a specific skeleton volume ranging from 0.129 cc/g to 0.130 cc/g while 3BS positive active material paste 60 with 1% TiCh additives has a specific skeleton volume of 0.124 cc/g.
  • control 4BS positive active material paste 60 with no TiCh additives has a specific skeleton volume of 0.131 cc/g while 4BS positive active material paste 60 with 1% TiCh additives has a specific skeleton volume ranging from 0.124 cc/g to 0.125 cc/g.
  • control 3BS positive active material paste 60 with no TiCh additives has a specific pore volume ranging from 0.088 cc/g to 0.090 cc/g while 3BS positive active material paste 60 with 1% TiCh additives has a specific pore volume ranging from 0.107 cc/g to 0.108 cc/g.
  • control 4BS positive active material paste 60 with no TiCh additives has a specific pore volume of 0.101 cc/g while 4BS positive active material paste 60 with 1% TiCh additives has a specific pore volume ranging from 0.137 cc/g to 0.142 cc/g.
  • Figure 3 also shows the porosity of the positive active material paste 60.
  • control 3BS positive active material paste 60 with no TiCh additives has a porosity ranging from 40.2% to 41.1% while 3BS positive active material paste 60 with 1% TiCb additives has a porosity ranging from 46.3% to 46.7%.
  • control 4BS positive active material paste 60 with no TiCh additives has a porosity ranging from 43.4% to 43.5% while 4BS positive active material paste 60 with 1% TiCh additives has a porosity ranging from 52.4% to 53.2%.
  • TiCb additives can therefore increase the porosity of the positive active material paste 60.
  • Figure 4 is a graph of a high-rate cycling test comparing a flooded deep cycle lead-acid electrode containing control positive active material paste with no TiCh additives to one containing positive active material paste with 1% rutile TiCh additive.
  • Figure 4 demonstrates that an electrode containing rutile TiCh with a weight percent between 0.1% to 4% of oxide load maintains a higher discharge capacity over more cycles than the control, lacking the rutile TiCh additive to the positive active material paste.
  • Figure 5 is a graph of a cycle life test comparing flooded deep cycle lead-acid batteries 10 containing 3BS control positive active material paste 60 with no TiCh additives to flooded deep cycle lead-acid batteries 10 containing 3BS positive active material paste 60 with 1% rutile TiCh additives.
  • there is a clear difference in the antimony suppression effect which is the suppression of the lead antimony alloy’s tendency to leach out of the positive plate 70 and migrate to the negative plate 90 causing a higher end of charging current value (EoCC).
  • the antimony suppression effect is significantly better in the flooded deep cycle lead-acid batteries 10 containing 3BS positive active material paste 60 with 1% rutile TiCb additives than the flooded deep cycle lead-acid batteries 10 containing 3BS control positive active material paste 60 with no TiCh additives. Further, the cycle life of the flooded deep cycle lead-acid batteries 10 appears to be significantly extended in the flooded deep cycle lead-acid batteries 10 containing 3BS positive active material paste 60 with 1% rutile TiCh additives as compared to the flooded deep cycle lead-acid batteries 10 containing 3BS control positive active material paste 60 with no TiCh additives.
  • Figure 6 is a graph of a cycle life test comparing flooded deep cycle lead-acid batteries 10 containing 4BS control positive active material paste 60 with no TiCh additives to flooded deep cycle lead-acid batteries 10 containing 4BS positive active material paste 60 with 1% rutile TiCh additives. As shown in Figure 5, there is significant initial capacity and peak capacity improvement in the flooded deep cycle lead-acid batteries 10 containing 4BS positive active material paste 60 with 1% rutile TiCh additives.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Batterie plomb-acide à cycle profond inondée comprenant au moins une plaque négative, au moins une plaque positive et un électrolyte. La plaque positive comprend une grille d'électrode positive constituée principalement de plomb et d'une pâte positive comprenant un composé de plomb et un additif de dioxyde de titane (TiO2). Un procédé de fabrication d'une pâte de matériau actif positif pour une batterie plomb-acide à cycle profond inondée comprend les étapes suivantes : ajout direct de TiO2 dans un mélangeur de pâte avec un composé de plomb pour constituer un mélange d'additifs positifs ; mélange à sec des additifs positifs pour constituer un mélange sec ; ajout d'eau au mélange sec ; mélange humide de l'eau avec le mélange sec pour constituer un mélange humide ; collage et durcissement d'une grille d'électrode positive à l'aide du mélange humide.
PCT/US2023/029677 2022-08-10 2023-08-08 Dioxyde de titane dans les batteries plomb-acide à cycle profond inondées Ceased WO2024035663A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP23853262.6A EP4569555A2 (fr) 2022-08-10 2023-08-08 Dioxyde de titane dans les batteries plomb-acide à cycle profond inondées

Applications Claiming Priority (2)

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US202263370982P 2022-08-10 2022-08-10
US63/370,982 2022-08-10

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WO2024035663A2 true WO2024035663A2 (fr) 2024-02-15
WO2024035663A3 WO2024035663A3 (fr) 2024-04-18

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Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302476A (en) * 1990-12-03 1994-04-12 Globe-Union Inc. High performance positive electrode for a lead-acid battery
US20180047990A1 (en) * 2016-08-09 2018-02-15 Trojan Battery Ireland Ltd. Metal oxides in lead-acid batteries

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WO2024035663A3 (fr) 2024-04-18
EP4569555A2 (fr) 2025-06-18

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